WO2004056920A2 - Foamed materials rendered barely combustible using ammonium sulfate and other flameproofing agents - Google Patents
Foamed materials rendered barely combustible using ammonium sulfate and other flameproofing agents Download PDFInfo
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- WO2004056920A2 WO2004056920A2 PCT/EP2003/011538 EP0311538W WO2004056920A2 WO 2004056920 A2 WO2004056920 A2 WO 2004056920A2 EP 0311538 W EP0311538 W EP 0311538W WO 2004056920 A2 WO2004056920 A2 WO 2004056920A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3054—Ammonium sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
Definitions
- Foams have been known for a long time and are widely used due to their low density and the associated material savings, their excellent thermal and acoustic insulation properties, their mechanical damping and their special electrical properties.
- foams can be found in packaging, in furniture and mattresses, generally for sound and heat insulation, as buoyancy bodies in watercraft, as filter and carrier material in various industrial sectors and as structural elements in the production of layered materials, laminates, composites or foam composites.
- adequate fire protection of the foams is necessary, as is the case in legal ones Regulations and a number of other regulations is required.
- the foams should not contain any toxic and / or odor-causing cleavage products, as is the case, for example, when using some phosphorus compounds as flame retardants.
- AMSU as a flame retardant in isocyanate-based foams
- German patent application DE 2542048 The foams described there were made self-extinguishing by means of the finely ground AMSU.
- a foam containing 19% by weight of AMSU burned for a short time after being removed from a Bunsen burner flame and then went out. At 20.9% by weight of AMSU, the foam went out immediately after being removed from the flame.
- European patent application EP 347497 flame-retardant, polyurethane-based foams are also described in European patent application EP 347497 flame-retardant, polyurethane-based foams.
- German patent application No. 10241855.1 describes AMSU as a flame retardant for PMI foams.
- the smoke density test according to FAR 25.853 (c) was also passed.
- AMSU Compared to other flame retardants, the use of AMSU has the following advantages: It is cheap and can be worked into materials inexpensively as an insoluble solid. Since it is completely non-toxic, people are not endangered neither in handling nor in processing. For the same reason, there are no additional risks when processing foams equipped with AMSU, for example due to dust. AMSU is used in large quantities as a fertilizer. The entry of small amounts of AMSU into the environment is therefore ecologically harmless. There are also no additional problems with the disposal of waste materials due to the use of foams equipped with AMSU, ie the disposal of waste materials is possible using the usual disposal methods. As an inorganic solid, AMSU is not soluble in the plastic matrix. This gives the additional great advantage over soluble flame retardants that it does not act as a plasticizer.
- AMSU as a flame retardant
- no foams based on PVC, blends made of PVC and PU, PEI and SAN have been described in the literature known hitherto other flame retardants has been improved.
- the incorporation of AMSU offers the possibility of achieving very good flame protection for all of the foams mentioned.
- the effect of ammonium sulfate is similar to that of ammonium polyphosphate. It is based on the decay of the crystalline Compound in ammonia and sulfuric acid at a higher temperature. The released sulfuric acid has a pyrolyzing effect, while the released ammonia gas dilutes the flammable gases and therefore has an extinguishing effect.
- JP 08325574 describes combinations of flame retardants which also contain ammonium sulfate, among other things.
- the compositions described there are suitable for casting resins.
- Combinations of other flame retardants with ammonium polyphosphate are also deposited, for example, in patent CN 1197103.
- Other applications described in the literature which are flame-retardant with ammonium sulfate include textile applications (Khattab, MA; Gad, AM; El-Samanoudi, AHJ Appl. Polym. Sc .: Appl. Polym. Symp. (1994), 55, 87-96; Basch, Avraham; Lewin, Menachem, Text. Res. J.
- AMSU is used as a flame retardant for paper (JP 11228968), for wood (JP 11105011; DE 19748751; Hsieh, Tang-Chou, Tai-wan Lin Yeh Shi Yen So Pao Kao (1970), No. 188, 22 pp .; Zakl. Konserw. Drewna, Pr. Inst. Technol. Drewna (1969), 16 (3), 115-28) and for polymeric materials such as polystyrene (JP 05086254) and polyethylene, polypropylene or their copolymers (AU Vasil'ev, Yu.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
Neue, schwer brennbare Schaumstoffe unter Verwendung von Ammoniumsulfat und anderen FlammschutzmittelnNew, flame-retardant foams using ammonium sulfate and other flame retardants
Anwendungsgebiet der ErfindungField of application of the invention
Zusammensetzungen von Schaumstoffen mit verminderter EntflammbarkeitFoam compositions with reduced flammability
Stand der TechnikState of the art
Die vorliegende Erfindung betrifft Zusammensetzungen von Schäumen mit verbessertem Flammverhalten auf der Basis von Polyetherimid (PEI), von Styrol-Acrylnitril Copolymeren (SAN), von Polyvinylchlorid (PVC), von Blends aus PVC und Polyurethanen (PU) oder von Phenolharzen. Aus den genannten Materialien können durch verschiedene Methoden Schäume hergestellt werden, zum Beispiel durch Einarbeitung eines Treibmittels in das Polymermaterial, durch Schlagen einer Polymerschmelze, durch die Einarbeitung von Hohlkugeln (sog. syntaktische Schäume) oder durch eine Kombination dieser Prozesse. Das Flammverhalten dieser Schäume wird durch die Einarbeitung von möglichst fein vermahlenem Ammoniumsulfat (AMSU) entscheidend verbessert.The present invention relates to compositions of foams with improved flame behavior based on polyetherimide (PEI), styrene-acrylonitrile copolymers (SAN), polyvinyl chloride (PVC), blends made of PVC and polyurethanes (PU) or phenolic resins. Various methods can be used to produce foams from the materials mentioned, for example by incorporating a blowing agent into the polymer material, by beating a polymer melt, by incorporating hollow spheres (so-called syntactic foams) or by a combination of these processes. The flame behavior of these foams is decisively improved by incorporating the finest possible ground ammonium sulfate (AMSU).
Schaumstoffe sind seit langer Zeit bekannt und finden wegen ihrer geringen Dichte bzw. der damit verbundenen Materialersparnis, ihren hervorragenden thermischen und akustischen Isolationseigenschaften, ihrer mechanischen Dämpfung sowie ihren besonderen elektrischen Eigenschaften eine breite Anwendung. So findet man Schaumstoffe in Verpackungen, in Möbeln und Matratzen, allgemein bei der Schall- und Wärmeisolation, als Auftriebskörper in Wasserfahrzeugen, als Filter- und Trägermaterial in verschiedenen Industriebereichen und als Strukturelemente bei der Herstellung von Schichtwerkstoffen, Laminaten, Composits oder Schaumstoffverbundkörpern. Für viele Anwendungen gerade im Bau von Luft- und Wasserfahrzeugen ist ein ausreichender Brandschutz der Schaumstoffe notwendig, wie er in gesetzlichen Vorschriften und einer Reihe anderer Regelwerke gefordert wird. Der Nachweis, dass die Schaumstoffe den brandschutztechnischen Anforderungen genügen, wird mit Hilfe einer Vielzahl unterschiedlicher Brandschutzprüfungen geführt, welche üblicherweise auf die Anwendung des Schaumstoffes bzw. des diesen enthaltenden Verbundkörpers ausgerichtet sind. Im allgemeinen müssen Schaumstoffe mit so genannten Flammschutzmitteln ausgerüstet werden, damit diese Brandschutzprüfungen bestanden werden. Weithin ist die Verwendung von chlor- oder bromhaltigen Verbindungen als Flammschutzmittel bekannt, die häufig in Kombination mit Antimonoxiden eingesetzt werden. Nachteilig ist hierbei jedoch, dass Kunststoffe und Schaumstoffe, deren Entflammbarkeit hierdurch vermindert ist, äußerst schlecht recyclebar sind, da diese Halogenkohlenwasserstoffe kaum aus dem Polymer abgetrennt werden können und in Müllverbrennungsanlagen aus diesen Verbindungen Dioxine entstehen können. Darüber hinaus werden im Brandfall giftige und korrosive Gase, wie beispielsweise HCI und HBr, gebildet. In der europäischen Patentanmeldung EP 347497 wird darüber hinaus festgestellt, dass halogen- und phosphorhaltige niedermolekulare Flammschutzmittel in isocyanatbasierten Schäumen nur in Brandtests im Labormaßstab und nicht unter Bedingungen, die einem Brandfall entsprechen, getestet wurden. Aufgrund oben genannter Nachteile ist es allgemeines Ziel, chlorierte und bromierte Substanzen als Additive in Kunststoffen möglichst zu vermeiden.Foams have been known for a long time and are widely used due to their low density and the associated material savings, their excellent thermal and acoustic insulation properties, their mechanical damping and their special electrical properties. For example, foams can be found in packaging, in furniture and mattresses, generally for sound and heat insulation, as buoyancy bodies in watercraft, as filter and carrier material in various industrial sectors and as structural elements in the production of layered materials, laminates, composites or foam composites. For many applications, especially in the construction of aircraft and water vehicles, adequate fire protection of the foams is necessary, as is the case in legal ones Regulations and a number of other regulations is required. Evidence that the foams meet the fire protection requirements is carried out with the aid of a large number of different fire protection tests, which are usually aimed at the use of the foam or the composite body containing it. In general, foams must be equipped with so-called flame retardants in order to pass these fire protection tests. The use of chlorine- or bromine-containing compounds as flame retardants, which are often used in combination with antimony oxides, is widely known. The disadvantage here, however, is that plastics and foams, the flammability of which is reduced as a result, are extremely difficult to recycle, since these halogenated hydrocarbons can hardly be separated from the polymer and dioxins can be formed from these compounds in waste incineration plants. In addition, toxic and corrosive gases such as HCI and HBr are formed in the event of a fire. European patent application EP 347497 also states that halogen and phosphorus-containing low-molecular flame retardants in isocyanate-based foams have only been tested in fire tests on a laboratory scale and not under conditions which correspond to a fire. Because of the disadvantages mentioned above, the general aim is to avoid chlorinated and brominated substances as additives in plastics as far as possible.
Phosphorverbindungen sind eine weitere Substanzklasse von Flammschutzmitteln, mit denen Schaumstoffe ausgerüstet werden. Nachteilig ist hierbei insbesondere, dass im Brandfall wie auch bei halogenhaltigen Flammschutzmitteln eine sehr hohe Rauchgasdichte entsteht. Wegen der Giftigkeit der Rauchgase und der Sichtbehinderung durch den Rauch werden Personen in der Umgebung des Brandes, insbesondere in geschlossenen Räumen, gefährdet und Rettungsarbeiten erschwert. Des weiteren wirken niedermolekulare Verbindungen, zu denen viele halogen- und phosphorhaltige Flammschutzmittel zählen, in vielen Kunststoffen als Weichmacher. Diese unerwünschte Wirkung verschlechtert die mechanischen Eigenschaften und begrenzt so den möglichen Anteil des Flammschutzmittels am Material. Mit der Menge sind auch der auf diesem Wege erzielbaren Flammschutzwirkung Grenzen gesetzt. Darüber hinaus besteht bei niedermolekularen Verbindungen die Gefahr, dass diese mit der Zeit aus dem Material herausdiffundieren. Hierdurch verschlechtert sich einerseits das Flammverhalten des Materials, andererseits kommt es zu einem eventuell unerwünschten Eintrag des Flammschutzmittels in die Umgebung.Phosphorus compounds are another class of flame retardants with which foams are treated. A particular disadvantage here is that in the event of a fire, as well as with halogen-containing flame retardants, a very high smoke gas density is produced. Because of the toxicity of the smoke gases and the visual impairment caused by the smoke, people in the vicinity of the fire, especially in closed rooms, are endangered and rescue work is made more difficult. In addition, low-molecular compounds, to which many halogen and phosphorus-containing flame retardants count as plasticizers in many plastics. This undesirable effect deteriorates the mechanical properties and thus limits the possible proportion of the flame retardant in the material. The quantity also limits the flame retardancy that can be achieved in this way. In addition, there is a risk with low molecular weight compounds that they will diffuse out of the material over time. As a result, the flame behavior of the material deteriorates, on the one hand, and the flame retardant may possibly enter the environment in an undesirable manner.
Aufgabetask
In Anbetracht des hierin angegebenen und diskutierten Standes der Technik war es Aufgabe der vorliegenden Erfindung, Zusammensetzungen zur Herstellung von Polymerschaumstoffen mit verminderter Entflammbarkeit, einer geringen Rauchentwicklung (z.B. FAR 25.853 (c) und AITM 2.0007), sowie einer geringen Wärmeentwicklung (z.B. FAR 25.853(c) ) anzugeben. Weiterhin sollen die Schaumstoffe keine giftigen und/oder geruchsbelästigenden Spaltprodukte enthalten, wie es beispielsweise bei der Verwendung einiger Phosphorverbindungen als Flammschutzmittel der Fall ist. Aus den oben genannten Gründen war es Aufgabe der Erfindung, Zusammensetzungen für Schaumstoffe anzugeben, deren Flammverhalten ohne den Einsatz halogenierter Flammschutzmittel verbessert wird. Des weiteren lag der Erfindung die Aufgabe zugrunde, einen möglichst kostengünstigen Flammschutz für die genannten Schaumstoffe anzugeben. Mithin war es Aufgabe der vorliegenden Erfindung, dass das zur Ausrüstung verwendete Flammschutzmittel gesundheitlich möglichst unbedenklich sein sollte und keine negativen Auswirkungen auf die Verarbeitbarkeit des ausgerüsteten Schaums haben sollte. LösungIn view of the prior art specified and discussed herein, it was an object of the present invention to provide compositions for the production of polymer foams with reduced flammability, low smoke development (e.g. FAR 25.853 (c) and AITM 2.0007), and low heat development (e.g. FAR 25.853 ( c)) to be specified. Furthermore, the foams should not contain any toxic and / or odor-causing cleavage products, as is the case, for example, when using some phosphorus compounds as flame retardants. For the reasons mentioned above, it was an object of the invention to provide compositions for foams whose flame behavior is improved without the use of halogenated flame retardants. Furthermore, the invention was based on the object of specifying the most cost-effective flame retardant for the foams mentioned. It was therefore an object of the present invention that the flame retardant used for the finishing should be as harmless to health as possible and should not have any negative effects on the processability of the finished foam. solution
Die genannte Aufgabe kann durch Schaumstoffe gelöst werden, deren Flammschutzeigenschaften durch festes Ammoniumsulfat (AMSU) in möglichst feiner Verteilung verbessert werden.The stated object can be achieved by means of foams whose flame retardant properties are improved by solid ammonium sulfate (AMSU) in the finest possible distribution.
Der Einsatz von AMSU als Flammschutzmittel in isocyanatbasierten Schäumen wurde zum Beispiel in der deutschen Patentanmeldung DE 2542048 beschrieben. Die dort beschriebenen Schaumstoffe wurden durch möglichst fein gemahlenes AMSU selbstverlöschend ausgerüstet. So brannte ein Schaum, der 19 Gew.% AMSU enthielt, nach dem Herausnehmen aus einer Bunsenbrennerflamme noch kurz nach und erlosch dann. Bereits bei 20,9 Gew.% AMSU erlosch der Schaum sofort nach dem Herausnehmen aus der Flamme. Auch in der europäischen Patentanmeldung EP 347497 flammgeschützte, polyurethanbasierte Schäume beschrieben. Aus den dort angeführten Beispielen ist der Vorteil der Verwendung von AMSU als Flammschutzmittel klar ersichtlich: Durch eine Steigerung des AMSU-Anteils von 15 auf 39 Gew.% des Gesamtmaterials konnte der LOI nach ASTM D-2863 von 24 auf 30 erhöht werden. Weitere Beispiele für AMSU-haltige Polyurethanschäume finden sich in US 3737400. Brennlänge und -zeit der dort diskutierten Hartschaumproben sanken durch Einarbeitung von 15,5 Gew.% AMSU und mehr auf null ab.The use of AMSU as a flame retardant in isocyanate-based foams has been described, for example, in German patent application DE 2542048. The foams described there were made self-extinguishing by means of the finely ground AMSU. A foam containing 19% by weight of AMSU burned for a short time after being removed from a Bunsen burner flame and then went out. At 20.9% by weight of AMSU, the foam went out immediately after being removed from the flame. Also described in European patent application EP 347497 flame-retardant, polyurethane-based foams. The advantage of using AMSU as a flame retardant is clearly evident from the examples given there: By increasing the AMSU content from 15 to 39% by weight of the total material, the LOI according to ASTM D-2863 could be increased from 24 to 30. Further examples of AMSU-containing polyurethane foams can be found in US 3737400. Burning length and time of the rigid foam samples discussed there decreased to zero due to the incorporation of 15.5% by weight of AMSU and more.
In der deutschen Patentanmeldung Nr. 10241855.1 wird AMSU als Flammschutzmittel für PMI-Schäume beschrieben. Ein PMI-Schaum aus 75 Gew.-Teilen AMSU als Flammschutzmittel auf ca. 110 Gew.-Teile sonstigem Material mit einem Raumgewicht von 82 kg/m3 zeigte eine Wärmefreisetzung von HR = 71 ,0 kWmin/m2 bzw. HRR = 64,2 kW/m2 gemäß FAR 25.853(c). Auch die Rauchgasdichteprüfung gemäß FAR 25.853(c) wurde bestanden. Demgegenüber setzte ein Schaum vergleichbaren Raumgewichts ohne AMSU Flammschutz mit HR = 102,0 kWmin/m2 bzw. HRR = 106,0 kW/m2 wesentlich mehr Wärme frei und zeigte auch eine schlechtere Rauchgasentwicklung. Gegenüber anderen Flammschutzmitteln hat die Verwendung von AMSU folgende Vorteile: Es ist billig und kann als unlöslicher Feststoff kostengünstig in Materialien eingearbeitet werden. Da es vollkommen ungiftig ist, werden Personen weder bei der Handhabung noch bei der Verarbeitung gefährdet. Aus demselben Grund ergeben sich keine zusätzlichen Gefahren bei der Verarbeitung von mit AMSU ausgerüsteten Schäumen z.B. durch Stäube. AMSU wird in großen Mengen als Düngemittel eingesetzt. Der Eintrag geringer Mengen AMSU in die Umwelt ist somit ökologisch unbedenklich. Auch bei der Altstoffentsorgung treten keine zusätzlichen Probleme durch die Verwendung von mit AMSU ausgerüsteten Schaumstoffen auf, d.h. die Beseitigung von Altstoffen ist über die gängigen Entsorgungswege möglich. AMSU ist als anorganischer Feststoff nicht in der Kunststoffmatrix löslich. Hieraus ergibt sich der zusätzliche große Vorteil gegenüber löslichen Flammschutzmitteln, dass es nicht als Weichmacher wirkt. Beim Einsatz von AMSU in PVC ergibt sich im Brandfalle der zusätzliche Vorteil, daß das aus PVC gebildete giftige Chlorwasserstoffgas durch den aus AMSU freigesetzten Ammoniak gebunden wird. Auch im Brandfall zeichnet sich Ammoniumsulfat durch seine nicht toxischen Eigenschaften aus, insbesondere wird die Rauchgasdichte besonders gering.German patent application No. 10241855.1 describes AMSU as a flame retardant for PMI foams. A PMI foam made from 75 parts by weight of AMSU as a flame retardant on approx. 110 parts by weight of other material with a density of 82 kg / m 3 showed a heat release of HR = 71.0 kWmin / m 2 or HRR = 64 .2 kW / m 2 according to FAR 25.853 (c). The smoke density test according to FAR 25.853 (c) was also passed. In contrast, a foam of comparable density without AMSU flame retardant with HR = 102.0 kWmin / m 2 or HRR = 106.0 kW / m 2 released significantly more heat and also showed poorer smoke gas development. Compared to other flame retardants, the use of AMSU has the following advantages: It is cheap and can be worked into materials inexpensively as an insoluble solid. Since it is completely non-toxic, people are not endangered neither in handling nor in processing. For the same reason, there are no additional risks when processing foams equipped with AMSU, for example due to dust. AMSU is used in large quantities as a fertilizer. The entry of small amounts of AMSU into the environment is therefore ecologically harmless. There are also no additional problems with the disposal of waste materials due to the use of foams equipped with AMSU, ie the disposal of waste materials is possible using the usual disposal methods. As an inorganic solid, AMSU is not soluble in the plastic matrix. This gives the additional great advantage over soluble flame retardants that it does not act as a plasticizer. In the event of fire, the use of AMSU in PVC gives the additional advantage that the toxic hydrogen chloride gas formed from PVC is bound by the ammonia released from AMSU. Even in the event of a fire, ammonium sulfate is characterized by its non-toxic properties, in particular the smoke density is particularly low.
Trotz der enormen Vorteile von AMSU als Flammschutzmittel wurden in der bisher bekannten Literatur noch keine Schäume auf der Basis von PVC, von Blends aus PVC und PU, von PEI und von SAN beschrieben, deren Brandverhalten durch die Verwendung von AMSU oder durch Kombinationen von AMSU mit anderen Flammschutzmitteln verbessert wurde. Für alle genannten Schäume bietet die Einarbeitung von AMSU die Möglichkeit, einen sehr guten Flammschutz zu erzielen. Die Wirkung von Ammoniumsulfat ist ähnlich der des Ammoniumpolyphosphats. Sie beruht auf dem Zerfall der kristallinen Verbindung in Ammoniak und Schwefelsäure bei höherer Temperatur. Die freigesetzte Schwefelsäure wirkt pyrolysierend, während das freigesetzte Ammoniakgas die brennbaren Gase verdünnt und daher eine Löschwirkung hat. Nachzulesen ist dies beispielsweise in der Patentschrift JP 08325574, in der Kombinationen von Flammschutzmitteln beschrieben werden, die unter anderem auch Ammoniumsulfat enthalten. Die dort beschriebenen Zusammensetzungen sind für Gießharze geeignet. Kombinationen von anderen Flammschutzmitteln mit Ammoniumpolyphosphat sind beispielsweise auch im Patent CN 1197103 hinterlegt. Zu den sonstigen in der Literatur beschriebenen Anwendungen, die mit Ammoniumsulfat flammgeschützt sind, zählen Textilanwendungen (Khattab, M. A.; Gad, A. M.; El-Samanoudi, A. H. J. Appl. Polym. Sei.: Appl. Polym. Symp. (1994), 55, 87-96; Basch, Avraham; Lewin, Menachem, Text. Res. J. (1973), 43(11), 693-4), und auch Löschmittel für Waldbrände (WO 9858039; US 3409550). AMSU wird als Flammschutz für Papier (JP 11228968), für Holz (JP 11105011 ; DE 19748751 ; Hsieh, Tang- Chou, Tai-wan Lin Yeh Shi Yen So Pao Kao (1970), No. 188, 22 pp.; Zakl. Konserw. Drewna, Pr. Inst. Technol. Drewna (1969), 16(3), 115-28) und für polymere Werkstoffe wie beispielsweise Polystyrol (JP 05086254) und Polyethylen, Polypropylen oder deren Copolymeren (AU Vasil'ev, Yu. V.; Ryabinina, L. I.; Fil'bert, D. V., USSR, Sin. Volokna (1969), 69-71. Editor(s): Pakshver, A. V. Publisher: lzd.,"Khimiya", Moscow, USSR. , JP 48055942; JP 47034541) verwendet. Auch in Polyurethanschäumen hat Ammoniumsulfat als Flammschutzadditiv bereits Verwendung gefunden (US 5948148, US 3737400, Solodovnik, P. I.; Mel'nikov, V. M.; Putnins, E., USSR, Razrab. Metodov Tepl. Zashch. Inzh. Sooruzh. Krainem Sev. (1983), 133-41. Editor(s): Ivanov, N. S. Publisher: Yakutsk. Gos. Univ., Yakutsk, USSR.). Despite the enormous advantages of AMSU as a flame retardant, no foams based on PVC, blends made of PVC and PU, PEI and SAN have been described in the literature known hitherto other flame retardants has been improved. The incorporation of AMSU offers the possibility of achieving very good flame protection for all of the foams mentioned. The effect of ammonium sulfate is similar to that of ammonium polyphosphate. It is based on the decay of the crystalline Compound in ammonia and sulfuric acid at a higher temperature. The released sulfuric acid has a pyrolyzing effect, while the released ammonia gas dilutes the flammable gases and therefore has an extinguishing effect. This can be read, for example, in JP 08325574, which describes combinations of flame retardants which also contain ammonium sulfate, among other things. The compositions described there are suitable for casting resins. Combinations of other flame retardants with ammonium polyphosphate are also deposited, for example, in patent CN 1197103. Other applications described in the literature which are flame-retardant with ammonium sulfate include textile applications (Khattab, MA; Gad, AM; El-Samanoudi, AHJ Appl. Polym. Sc .: Appl. Polym. Symp. (1994), 55, 87-96; Basch, Avraham; Lewin, Menachem, Text. Res. J. (1973), 43 (11), 693-4), and also extinguishing agents for forest fires (WO 9858039; US 3409550). AMSU is used as a flame retardant for paper (JP 11228968), for wood (JP 11105011; DE 19748751; Hsieh, Tang-Chou, Tai-wan Lin Yeh Shi Yen So Pao Kao (1970), No. 188, 22 pp .; Zakl. Konserw. Drewna, Pr. Inst. Technol. Drewna (1969), 16 (3), 115-28) and for polymeric materials such as polystyrene (JP 05086254) and polyethylene, polypropylene or their copolymers (AU Vasil'ev, Yu. V .; Ryabinina, LI; Fil'bert, DV, USSR, Sin.Volokna (1969), 69-71.Editor (s): Pakshver, AV Publisher: lzd., "Khimiya", Moscow, USSR., JP 48055942 ; JP 47034541) is used. Ammonium sulfate has also already been used as a flame retardant additive in polyurethane foams (US 5948148, US 3737400, Solodovnik, PI; Mel'nikov, VM; Putnins, E., USSR, Razrab. Metodov Tepl. Zashch. Inzh. Sooruzh. Krainem Sev. (1983 ), 133-41.Editor (s): Ivanov, NS Publisher: Yakutsk.Gos.Univ., Yakutsk, USSR.).
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003298089A AU2003298089A1 (en) | 2002-12-19 | 2003-10-18 | Foamed materials rendered barely combustible using ammonium sulfate and other flameproofing agents |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10260096.1 | 2002-12-19 | ||
| DE2002160096 DE10260096A1 (en) | 2002-12-19 | 2002-12-19 | New, flame-retardant foams using ammonium sulfate and other flame retardants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2004056920A2 true WO2004056920A2 (en) | 2004-07-08 |
| WO2004056920A3 WO2004056920A3 (en) | 2004-12-09 |
Family
ID=32404079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2003/011538 Ceased WO2004056920A2 (en) | 2002-12-19 | 2003-10-18 | Foamed materials rendered barely combustible using ammonium sulfate and other flameproofing agents |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU2003298089A1 (en) |
| DE (1) | DE10260096A1 (en) |
| TW (1) | TW200417599A (en) |
| WO (1) | WO2004056920A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1907463A4 (en) * | 2005-07-01 | 2009-12-30 | American Thermal Holding Compa | Ultra-low petroleum plastics |
| EP2666626A1 (en) | 2012-05-23 | 2013-11-27 | Sekisui Alveo AG | Flame-retardant polyolefin foam and its production |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009025163A1 (en) * | 2009-06-12 | 2010-12-16 | Sto Ag | module |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB716424A (en) * | 1950-01-28 | 1954-10-06 | Equipment Menager Et Ind E M I | Improvements in or relating to methods of manufacturing cellular products |
| US3737400A (en) * | 1972-03-24 | 1973-06-05 | Toyo Rubber Chemical Ind Co | Self-extinguishable polyurethane foam |
| GB1486867A (en) * | 1976-04-23 | 1977-09-28 | Chloride Group Ltd | Porous sheet materials |
| WO1991006614A1 (en) * | 1989-11-06 | 1991-05-16 | Bhf-Chemie Brandhemmende Füllstoffe Gmbh | Additive for synthetic foam and a pressed timber material of lignocellulose-containing substances |
| US5418282A (en) * | 1989-11-06 | 1995-05-23 | Bhf-Chemie Brandhemmende Fullstoffe Gmbh | Method of manufacturing fire-resistant resin foam and wood particle boards or shaped bodies |
-
2002
- 2002-12-19 DE DE2002160096 patent/DE10260096A1/en not_active Withdrawn
-
2003
- 2003-10-18 WO PCT/EP2003/011538 patent/WO2004056920A2/en not_active Ceased
- 2003-10-18 AU AU2003298089A patent/AU2003298089A1/en not_active Abandoned
- 2003-11-21 TW TW92132716A patent/TW200417599A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1907463A4 (en) * | 2005-07-01 | 2009-12-30 | American Thermal Holding Compa | Ultra-low petroleum plastics |
| EP2666626A1 (en) | 2012-05-23 | 2013-11-27 | Sekisui Alveo AG | Flame-retardant polyolefin foam and its production |
| WO2013174482A1 (en) | 2012-05-23 | 2013-11-28 | Sekisui Alveo Ag | Flame-retardant polyolefin foam and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2003298089A1 (en) | 2004-07-14 |
| AU2003298089A8 (en) | 2004-07-14 |
| WO2004056920A3 (en) | 2004-12-09 |
| TW200417599A (en) | 2004-09-16 |
| DE10260096A1 (en) | 2004-07-01 |
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